The behavior of low index planes of copper single‐crystal electrodes, simultaneously exposed to deaerated and pre‐equilibrated acidic copper sulfate solution, has been studied. The surface topographies indicated that a small net dissolution reaction occurred, due to traces of oxygen present in the experimental system, in spite of all the purification steps applied. Potential differences between electrodes were within 1 mV. A low rate dissolution reaction occurred everywhere on the exposed surfaces of all specimens, but the extent of dissolution varied over the surface of the same specimen, indicating considerable heterogeneity of the metal crystal surfaces. The surface features formed during dissolution on all electrodes, like grooves, pyramidal pits, macro ledges, hillocks, etc., are consistently bounded by the {210}, {111}, and {100} planes. The application of Batterman's stability conditions indicates that these planes are slow dissolving and stable, under present experimental conditions. The crystallographic characteristics of these planes, in relation to the process of dissolution, are discussed. Mechanisms of formation of these surface features are proposed utilizing the terrace‐ledge‐kink model for metal crystal dissolution, and considering the effects of crystallographic structure, surface imperfections, and adsorbed inhibiting species on the step motion over the surface, for the given rate of dissolution.